Amides of 2-fluoro-2,2-dinitroethyl amines

ABSTRACT

Compounds of the formula   WHEREIN M AND N ARE INTERGERS BETWEEN 0 AND 3 INCLUSIVE PROVIDED THAT M + N IS NOT LESS THAN 1 NOR GREATER THAN 3 OR   ARE PREPARED BY CONTACTING COMPOUNDS OF THE FORMULA   WHERE R2 is allyl, benzyl or tert-butyl, with an acid. These secondary amines find use as plasticizers and additives in explosive compositions.

United States atent n 1 Adolph et al.

l l AMIDES OF 2-FLUORO-2,2-DINITROETHYL AMINES [75] Inventors: Horst G. Adolph, Beltsvillc. Md; William H. Gilligan, Washington, DC.

[73] Assignee: The United States of America as represented by the Secretary 0f the Navy, Washington. D.(.

[22 Filed: Jan. 28, 1971 [ll] Appl. No: 110.627

Prmmn ii.\amim'rLeland A. Sebastian .hmrner. Agent. or Firm-R S. Sciascia; J. A. Cooke 15?} ABSTRACT Lompounds of the formula Mar. 25, 1975 wherein R is C H hal) CH C F I N 2) N02 wherein m and n are intcrgcrs hctwccn and 3 inclusive provided that m n is not less than 1 nor greater than 3 or -C-CNH-CH2-C-F are prepared by contacting compounds of the formula F-CCH N-R where R is allyl, benzyl or tert-butyl, with an acid. These secondary amines find use as plasticizers and additives in explosive compositions.

12 Claims, N0 Drawings AMIDES OF 2-FLUORO-2.Z-DINITROETHYL AMINES BACKGROUND OF THE INVENTION This invention relates generally to chemical compounds and more particularly to amine derivatives which find use as plasticizers and/or additives in explosive compositions, and to a method for the preparation thereof.

As is well known in the art. it is desirable for an explosive composition to have as great an energy release on detonation per unit of weight as is possible so as to maximize efficiency. In order to achieve this result, it is often necessary to include energetic additives in the composition. However, the fact that a compound is highly energetic and can act as an explosive is not sufficient to enable one to use it as an additive in an explosive composition because it must also be thermally stable so that it will not decompose when exposed to moderate or high temperatures and must additionally be compatible with the other constituents of the explosive composition. Thus, continuing research in the explosive composition art is conducted to find materials which can be used as additives to explosive composi- Hon.

SUMMARY OF THE INVENTION .-\ccordingly. one object of this invention is to pro- HLIL highly energetic organic compounds.

Another object ofthis invention is to provide organic compounds that can be used as explosives.

A further object of this invention is to provide organic compounds that can be used as additives in explosive compositions.

A still further object ofthis invention is to provide organic compounds which are relatively thermally stable.

A further object of this invention is to provide organic compounds which are compatible with the other constituents used in explosive compositions.

A still further object of this invention is to provide a method for the preparation of these organic compounds.

Accordingly. these and other objects of this invention are accomplished by providing compounds of the formula F c CH2 u wherein R is selected from the group consisting of C H .1 C F wherein m and n are intergers between 0 and 3 inclusive provided that m n is not less than 1 nor greater than 3. and

which compounds are prepared by contacting compounds of the formula wherein R is selected from the group consisting of allyl, benzyl and tert-butyl or any other functional group capable of carbonium ion formation, with an acid.

DESCRIPTION OF THE PREFERRED- EMBODIMENT The compounds of this invention represented by the formula are readily prepared by contacting chemical intermediates of the formula with an acid. R represents a substituent which can be easily removed, generally via a carbonium ion intermediate, by treatment with acid. Although R can represent any of the commonly known groups that form a carbonium ion, the preferred values of R are tertbutyl, benzyl and allyl. The strength of the acid employed to effect the desired reaction is important in determining the rate. Thus the stronger acids will effect conversion more rapidly than weaker acids. Preferred acids include protic acids such as sulfuric or trifluoroacetic as well as Lewis acids such as BF or SnCl When an aprotic acid is used however it is necessary to hydrolyze the reaction mixture to obtain the desired product.

Similarly, although temperature is not a critical feature of this process, it will be recognized by those 65 skilled in the art that generally the higher the temperature the faster the reaction rate.

The chemical intermediates of this invention of the formula (1) F c CH2 N I are prepared by a number of different methods. Where R is in the above formula. one merely reacts fluorodinitromethane with a compound of the formula R N(CH- OR where R is lower alkyl. according to the procedure outlined in Patent application entitled "CHEMICAL" by William H. Gilligan, Ser. No. M01128. filed on the same date herewith. One can also obtain these intermediate compounds by reacting an amine of the formula F (:1 CH

r-c-cn F C CH2 NH R2 N02 with the appropriate acyl halide. acid anhydride or aromatic halogen of the formula (liqlln ha'ln rvo i while R represents a radial capable of forming a carbonium ion. R represents -cH, -CC-NCH -C-Fand II I II I I O O 0 R N0 (he'ln -int and R, represents I and -CH -C-F 4m The general nature of the invention have been set forth. the following examples are presented as specific illustrations thereof. It will be understood that the invention is not limited to these specific examples but is susceptible to various modifications that will be recognized by one of ordinary skill in the art.

EXAMPLE I B[S( 2-FLUORO-2,2-DINITROETHYL )AMlNE F (I CH F C CH2 A. About 8.!g crude N.N,-bis(2-lluoro-Z.Z- dinitroethyl) tcrt-butyaniine, the preparation of which is disclosed in Patent application entitled CHEMI- CAL" by William H. Gilligan. Ser. No. 110,628 filed on the same date herewith. was added to 30 ml conc. sul furic acid with stirring and cooling. After 2 hours at ambient temperature. the solution was poured on ice and the crude product recrystallized from methylene chloride-chloroform to give the desired product. m.p. 4445C.

B. A solution of 4.0g of N,N-bis(2-fluoro-2,2- dinitroethyl) benzylamine. the preparation of which is disclosed in Patent application entitled CHEMICAL" by William H. Gilligan Ser. No. 110,628 filed on the same date herewith, was dissolved in 10 ml oftrifluoroacetic acid and warmed to 60C. After adding 1 ml of concentrated sulfuric acid. the solution was allowed to cool to ambient temperature and stirred overnight. It was then poured on ice and the crude product purified as above in A to yield 2.8g of the desired product.

C. A solution of 2.42g N,N-bis(2-fluoro-2,2- dinitroethyl) benzylamine and 0.44 ml of TiCl in 3 ml carbon tetrachloride was heated at C for 2 days. The solution was cooled. diluted with methylene chloride. washed with dilute hydrochloric acid. dried and filtered. The solvent was evaporated in vacuo to give 1.6g of product.

5 6 EXAMPLE 2 It was then saturated with sodium sulfate, extracted 5 N,N-BlS(2-FLUORO-2,2-DINlTROETHYL)OXA- times with 50 ml portions of ether, dried and the sol- MIDE vent was then stripped. About 5 g of crude Z-fluoro- N CH c1 CO. COCl F-C-CH -NH-C-CH -ncI 9 N02 0 0 N02 I II II I F :-ca -t I-c-c-t;tcn -e-F H SO /CH CO0H N0 (cn c C(CH N0 N0 0 0 N0 I II II I About 16.8g of tert-butyl 2-fluoro-2,2-dinitroethyla- 2,2-dinitroethylformamide was obtained. The crude mine was dissolved in 50 ml of methylene chloride and 75 product was degassed and distilled in a molecular still cooled to 5-l0C. About 2.6g oxalyl chloride in ml at 0.1 mm/8090C to give the pure product. methvlene chloride was then added and the mixture was stirred for 1 hour at room temperature. Following EXAMPLE 4 this reaction mixture was heated to reflux for 6 hours N-(Z-FLUOROl NI T D and poured into dilute sulfuric acid. The organic sol- No rent was allowed to evaporate and then the residue was 2 filtered ivin 8.7 crude N.N'-ditert-butyl-N,N-bis(2- fluoro-fl-diiiitro thyl) oxamide. m.p. l59-l60C. F 5 CH2 NH 2 CH 2 About lUg of this product was added to 18 ml acetic No acid and [2 ml conc. sulfuric acid and stirred for 2 2 hours. After ice and water were added, the mixture was -0 filtered to give the desired product which was then recrystallized l'rom acetic acid; mp. 224C (dec.)v

Cl -0 EXAMPLE 3 0 N-( Z-FLUORO-lZ-DINITROETHYL) FORMAMIDE 2 F CH NH CH HCQOH /(CH CO) O5 N0 CH /C CH3 F C CH N conc H 80 CHO F C CH NH C H I 2 ll 2 60 10.5g tert-butyl 2-fluoro-2,2-dmttroethylamme was N02 dissolved in 30 ml formic acid and 30 ml acetic anhy- I dride was added. The mixture was stirred over night. 8C1 F c CH drowned in water and filtered thereby obtaining 8.5g a 2 2 tert-butyl 2-fluoro-2,Z-dinitroethyl l ormamide. About 2 9g of this material was added to 15 ml concentrated N N0 sulfuric acid and the mixture was stirred for about 6 hours at 25-30C. Thereafter the mixture was poured -02 onto crushed ice and diluted to ml with water. CH2 CH 2 Charcoal was added and the solution was then filtered.

A solution of 4.0g allyl fluorodinitroethylamine and 2.5g picryl chloride in 20 ml acetonitrile was heated to 70C for 24 hours and poured into dilute sulfuric acid. The drowning mixture was extracted with methylene chloride and the extracts were dried and freed from solvent. TLC analysis indicated the product to be a mixture of unreacted picryl chloride and N-allyl-N-(Z- fluoro-2.2-dinitroethyl) picramidev The two components were separated by chromatography on silica with methylene chloride as eluant. About 2.5g of product. free of starting material, was obtained. This product was stirred with concentrated sulfuric acid at ambient temperature for 24 hours and the entire mixture was then drowned on crushed ice. Upon recrystallizing from methylene chloride-hexane. 1.78g of N-(Z-fluoroll-dinitroethyl)picramide, m.p. l367C. was obtained.

In a similar manner whenever the other compounds or reactions herein described are desired, one only need follow the above procedures except that the appropriate starting materials should be substituted for the materials hereinbefore used.

Obviously. numerous modifications and variations of v the present invention are possible in light of the above teachings. lt is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.

What is claimed as new and desired to be secured by Letters Patent of the United States is:

1. Compounds of the formula wherein R is selected from the group consisting of H and wherein m and u are intergers between 0 and 3 inclusive provided that m n is not less than l nor more than 3.

N-(2fluoro-2.2-dinitroethyl) picramide.

4. Compounds of the formula F c ca N wherein R is selected from the group consisting of II II I -CH,-C-CNCH2-CF and II I I wherein m and u are intergers between 0 and 3 inclusive provided that m n is not less than 1 nor more than 3. and R is a group capable of forming a carbo nium ionv 5. A compound according to claim 4 wherein R is selected from the group consisting of t-butyl, benzyl and allyl.

6. A compound according to claim 5 wherein R is and R is t-butyl.

7. A compound according to claim 5 wherein R is -C-C-N II I I CH C-F and R is t-butyl.

8. A compound according to claim 5 wherein R is wherein R is selected from the group consisting of f2 2 -CH,-CH2-CF,C-CNH-CH2CF and Win II I n u l (na h 9 10 where m and n are intergers between and 3 provided wherein R is a group capable of forming a carbonium that m +n is not less than 1 nor more than 3 comprising ion, with an acid provided that when an aprotic acid is contacting a compound of the formula used water is added to the reaction mixture.

10. The process of claim 9 wherein R is selected N0 R 5 from the group consisting of allyl, benzyl and t-butyl. 11. The process of claim 9 wherein the acid is se- F C CH2 N lected from the group consisting of aprotic acids.

12. The process of claim 9 wherein the acid is a No R protic acid. 

1. COMPOUNDS OF THE FORMULA
 2. The compound of claim 1 which is N-(2-fluoro-2,2-dinitroethyl) formamide.
 3. The compound of claim 1 which is N-(2-fluoro-2,2-dinitroethyl) picramide.
 4. Compounds of the formula
 5. A compound according to claim 4 wherein R2 is selected from the group consisting of t-butyl, benzyl and allyl.
 6. A compound according to claim 5 wherein R3 is
 7. A compound according to claim 5 wherein R3 is
 8. A compound according to claim 5 wherein R3 is
 9. The process of preparing compounds of the formula
 10. The process of claim 9 wherein R2 is selected from the group consisting of allyl, benzyl and t-butyl.
 11. The process of claim 9 wherein the acid is selected from the group consisting of aprotic acids.
 12. The process of claim 9 wherein the acid is a protic acid. 